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Molecular tectonics: generation and structural studies on 1- and 2-D coordination networks based on a metacyclophane in 1,3-alternate conformation bearing four pyrazolyl units and cobalt, zinc and Copper cations
5

Jrme Ehrhart, Jean-Marc Planeix*, Nathalie Kyritsakas-Gruber and Mir Wais Hosseini*
Receipt/Acceptance Data [DO NOT ALTER/DELETE THIS TEXT] Publication data [DO NOT ALTER/DELETE THIS TEXT] DOI: 10.1039/b000000x [DO NOT ALTER/DELETE THIS TEXT] The combination of a [1111]metacyclophane blocked in 1,3-alternate conformation and bearing four pyrazolyl coordinating units with MX 2 (M = Co, Zn and X= Cl or Br) leads to the formation of porous crystals formed by packing of 2-D coordination networks. In the case of CuBr 2, the formation of a 1-D network was observed. Structural studies by X-ray diffraction methods on single crystals was performed on all cases reported .

10

Introduction
15

and 2-D coordination networks based on the combination of a [1111]metacyclophane backbone bearing four pyrazolyl units 2 (scheme) with metal cations (Zn (II), Co (II) and Cu (II).
40

Since the pioneering work by R. Robson et al,1 coordination polymers or MOFs, periodic architectures based on organic and metallic tectons,2,3 are attracting considerable interest. The craze for this class of solids results from its potential applications, in particular for separation, storage and catalysis.4 As stated above,

Results and discussion

X

20

coordination networks are based on iterative formation of coordination bonds between organic units and metal centres. In other terms, both the organic construction units and the metallic centres upon mutual interactions are structural nodes of the network. The formation of such assemblies results from the
N N N N

X 1 X = CH2Cl N N N N

N N N

25

interconnection of organic tectons bearing at least two divergently oriented coordinating sites and metal centres or complexes offering at least two free coordination sites also
45

N 2 N

Scheme
As stated above, the generation of coordination networks is based on the formation of coordination bonds??????? leading to structural nodes and its iteration generating the periodicity. The latter process requires divergent orientation of coordination sites on the organic
50

divergently oriented. One of the characteristics associated with coordination networks is the dimensionality (1-, 2- or 3-D). The
30

latter, defined by the number of independent translations operating at the level of the structural nodes, in principle may be controlled by both characteristics of the organic and metallic tectons. Pursuing our investigation on the design and formation of new

tecton. Another important factor associated with the design of networks is the rigidity of the construction units employed which often determine the predictability of the construction process. Taking into account these two features, the [1111]metacyclophane backbone is of particular interest. Indeed, for this type of cyclic platform,

35

coordination networks, we describe in this contribution the design, synthesis and structural investigations of a series of 1Laboratoire de Chimie de Coordination Organique (UMR CNRS 7140), Universit de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000 Strasbourg, France. Fax: 33 390241325; Tel: 33 390241323; E-mail: hosseini@chimie.u-strasbg.fr

55

among the four possible isomers, the 1,3-alternate conformation is the most stable one in solution over a wide range of temperature (60C to 150 C) implying a high rigidity of the squeleton.6

Furthermore, in the solid state, its blocked 1,3-alternate conformation was established by X-ray diffraction on single
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60

crystals for a variety of derivatives such as tetrahydoxyl6, tetracyano bipyridine

7

Owing to the distance of ca 7.0 between the two CH2 groups

90

and tetramercapto , tetrapyridine, and tetrakis quinoline

12

9,10

tetrakis
13

located on the same face of the molecule and the bent angle imposed by the connection of the pyrazolyl unit through its N atom, the tecton 2 (Fig. 2) should generate periodic architectures when associated with appropriate metal centres. However, although the [1111]metacyclophane backbone is intrinsically rigid, the introduction of the methylene group between its phenyl group and the pyrazolyl unit and the rotational freed resulting from the single C-N bond render the tecton 2 rather flexible. Indeed, depending on the orientation of the pyrazolyl and methylene groups (each may adopt two extreme orientations with respect to the backbone: towards the centre (i) or periphery (o)), several extreme rotamers may coexist. Figure 2 shows a demonstrative example of one of the rotamers (CiNi,CoNo,CiNo,CoNi).

11

tetraimidazolyl

derivatives as well as for its disubstituted derivatives.14 Taking advantage of this rigid and blocked conformation, one
65

may introduce up to four coordinating sites located two-bytwo on both faces of the main plane of the backbone. In order to avoid the formation of discrete metallamacrotricycles (Fig. 1 b), as we have previously demonstrated for the tetrakis imidazolyl derivative (compound 3, scheme)
13
95

and to promote

70

the formation of infinite networks (Fig. 1d and e), the pyrazolyl unit was chosen. The latter was connected to the cyclophane backbone by a C-N bond using a methylene group as spacer between the aromatic moiety and the coordinating unit. This design principle is based on our previous investigations on the formation of infinite 1-D tubular coordination networks (Fig. 1d) generated upon combining the [1111]metacyclophane bearing pyridyl,9,10 or cyanophenyl7 groups with silver cation. We15 and others16 have previously used the pyrazolyl moiety as a coordinating site for the design of tectons and the formation of coordination networks.
100

75

80

105

Figure 2: Owing to the rotational freedom of the C-CH2 and CH2N bonds, compound 2 blocked in 1,3-alternate conformation may adopt several rotamers. Here, the CiNi,CoNo,CiNo,CoNi rtotamer is
110

schematically represented (i = in; o = out with respect to the centroid of the backbone), The red plane represents the maine plane of the cyclophane.

The synthesis of 2 (Scheme) was achieved in 73 % yield upon

115

condensation of the chlorinated precursor 117 with sodium pyrazolate, generated in situ by treatment of pyrazol with sodium hydride, in DMF at 95 C and in the presence of catalytic amounts of NaI (see experimental section). The 1,3-alternate

Figure
85

1:

Schematic

representation

of

discrete
120

conformation of compound 1 was established by X-Ray diffraction on single crystals.17 As expected, the synthetic step performed did not alter the 1,3-alternate conformation of the free tecton 2 as verified in the solid state by X-Ray diffraction on single crystal (See experimental section, and Fig. 3).
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metallamacrocycles (b) formed by the (i,i,i,i) rotamer (a) of 3 and of 1-D (d) and 2-D (e) infinite coordination networks generated by combining the (o,o,o,o) rotamer (c) of 2 with tetra coordinated metal centres bearing two free coordination sites.
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The compound 2 is a neutral ligand. In order to generate neutral

125

Co2+ and Zn2+; X= Cl- and Br- and CuBr2). In all cases, the crystal structures of the coordination networks have been studied by X165

coordination networks, the ligand 2 was combined with neutral metal complexes offering two free coordination sites. Thus, metal halide MX2 type complexes were used. Whereas the combination of 2 with MX2 (M = Co , Zn ; X= Cl , Br ) afforded four isostructural 2-D coordination networks, in the case of CuBr2 a 1D metallaorganic architecture was obtained (see experimental section). Structural investigations: The solid state structure of the free tecton 2 was investigated by X-ray diffraction on single crystal. The crystal (Triclinic, Space group P-1), in addition to the ligand 2 contains 0.5 CHCl3 solvent molecules. The structural determination (see experimental section) confirmed the 1,3-alternate conformation of the tecton 2 (Fig. 3). The four pyrazolyl units connected to the cyclophane backbone through methylene junctions (dC-C in the range of 1.51 1.52 , dC-N in the range of 1.45 - 1.46 , CNC angle in the range of 124.5 - 126.3). Among the four pyrazolyl units (dCN in the range of 1.45 - 1.46 ; dNN in the range of 1.34 - 1.35 and NCN angle in the range of 129.0 130.0), three are oriented outwardly and one inwardly (NiNiNiNo isomer) with respect to the interior of the backbone. When taking into account both the orientation of the pyrazolyl and methylene groups, in the solid state the CoNi,CiNo,CoNi,CoNi rotamer is observed (see Fig. 2 for notation). The nitrogen atoms (secondary) of two pyrazolyl moieties located on the same face of the molecule are distant by 8.49 and 10.94 .
190 185 180 175 170

Ray diffraction on single crystals (see experimental section and Fig. 4, 5 and 7). For [2-(MX2)]n (M = Co2+ and Zn2+; X = Cl or Br) (Fig. 4-6), the X-ray studies revealed the formation of isostructural 2-D networks. Although all four structures are discussed bellow, we shall only present graphically the 2-D networks obtained with CoCl2 (Fig. 4) and ZnCl2 (Fig. 5). For all four cases, the crystal system is Orthorhombic with Pbcn as space group. In all cases, the crystal contains disordered solvent molecules (see experimental section). Whereas in the case of Co based network the solvent mixture was dichloroethane-ethanol, for the Zn based coordination polymer, a mixture of dichloroethane-methanol was found. Owing to the disorder and rapid loss of solvent molecules, their proportion could not be precisely determined and the squeeze command18 was used for the structural resolution. Thus, although the metric precision is low, the connectivity pattern however remains reliable. Although the same type of architecture (Fig. 1e) is obtained in all 4 cases, as expected, the bond distances and angles are different for each network (Tab. 1). The tecton 2 adopts the CoNi,CoNi,CoNi,CoNi conformation (all four pyrazolyl units are outwardly oriented and for each pyrazolyl unit, the coordinating N atom is inwardly positioned). In other terms, the only difference between the free tecton 2 (Fig. 3) and engaged ones in 2-D networks, is based on the rotation of one of the four pyrazolyl groups. Both Co (II) and Zn (II) cations adopt distorted tetrahedral coordination geometry (for angles see Tab. 1). Their coordination sphere is composed of two halides (Cl or Br) and two N atoms belonging to pyrazolyl moieties of consecutive tectons 2 (for dM-N and dM-X see Tab. 1) leading thus to neutral nodes. The 2-D networks thus formed are neutral and generated upon mutual bridging between tectons 2 and metal centres.
Table 1: Average bond distances () and angles ()

2+

2+

130

135

140

145

150

195

155

Fig. 3: The solid state structure of free 2 showing the blocked 1,3alternate conformation of the cyclophane backbone. Compound 2 is present as its CoNi,CiNo,CoNi,CoNi rotamer (see Fig. 2 for notation). For sake of clarity, H atoms and solvent molecules are omitted. For bond distances and angles see text.

M Co Co X Cl Br dN-M () 1.95 2.00 dX-M () 2.00 2.37 NMN () 102.0 103.5 XMX () 114.0 113.2
200

Zn Cl 2.00 2.24 101.2 115.0

Zn Br 2.00 2.39 101.6 115.2

160

For the 2-D networks formed with (CoCl2) (Fig. 4) and (CoBr2), as expected, both dN-Co and dX-Co distances are increased upon substitution of chloride by bromide anion. However, a slight
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The ability of tecton 2 to generate infinite coordination networks was investigated by combining 2 with metal halides (MX2, M =
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increase in distance between two cobalt centres located on the same face of the cyclophane is observed (dCo-Co = 11.12 for
205

chloride and dCo-Co = 11.14 for bromide).

230

Fig. 6: Representation (CPK model) of a portion of the structure of the crystal obtained upon combining 2 with CoCl2. Showing the packing along the c axis of two consecutive 2-D networks. For sake of clarity, the
235

two networks are differentiated by the colour of C atoms. H atoms and solvent molecules are omitted for clarity.

Fig. 4: A portion of the 2-D coordination network (view along the c axis) generated upon combining the tecton 2 with CoCl2. H atoms and solvent
210

The porosity of all four crystals was analysed using the platon software (see Tab. 2). A free volume per unit cell was of ca 50.%
240

molecules are omitted for clarity. For bond distances and angles see text. For the 2-D networks formed with (ZnCl2) (Fig. 5) and (ZnBr2),

was calculated for all four crystals studied. . Table 2: Cell volume and solvent area volume calculated using Platon software.18
Table 1: Porosity characteristic of the four crystalline materials obtained

whereas in average the same dN-Zn distance (2.00 ) is observed for both cases, the dX-Zn distance is increased when chloride is
215

replaced by bromide anion (Tab. 1). Compared to the network based on Co cation, the increase in distance between two zinc cations located on the side of the macrocycle is substantially higher (dZn-Zn = 10.33 for chloride and dZn-Zn = 11.13 for bromide).
245

upon combining the tecton 2 with (MX2) (M = Co

2+

and Zn2+; X =

Cl or Br). M X Unit Cell volume (3) Total Potential Solvent Area Vol (3)* Free volume per unit cell (%) Co Cl 8797.1 4481.0 50.9 Co Br 8945.9 4573.2 51.1 Zn Cl 8769.9 4401.4 50.2 Zn Br 8947.1 4525.9 50.6

* Calculated by Platon software 18

The TGA analysis on crystals containing 2 and CoCl2 or ZnCl2

250 220

revealed two intermediate regimes, the first one between 30 and 100 C and the second one between 100 and 200C, prior to decomposition of the samples which appeared at ca 350 C (Fig. 6). The first loss of masse corresponds to the release of the alcohol (EtOH in the case of cobalt and MeOH in the case of zinc) solvent molecules and the second one to the release of dichloroethane. In the case of [2-(ZnCl2)]n, owing to the lower boiling point of MeOH with respect to EtOH present in crystals

Fig. 5: A portion of the 2-D coordination network (view along the c axis) generated upon combining the tecton 2 with ZnCl2. H atoms and solvent molecules are omitted for clarity. For bond distances and angles see text.
255

225

The consecutive 2-D networks are packed along the c axis. However, the packing mode is of the type ABA with staggered arrangement of consecutive sheets (Fig. 6). This mode of packing generates pores which are occupied by solvent molecules.
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based on [2-(ZnCl2)]n networks, the slop of the solvent release in the 30 -100 C range was steeper as expected.
260 295

P2/c) is composed of tecton 2, CuBr2 and EtOH and dichloroethane solvent molecules. The latter are disordered and the diffraction power of the crystal appeared to b rather low. For the structural resolution the squeeze command was used.18 Consequently, the quality of resolution was rather low. The tecton 2 adopts the CoNi,CoNo,CoNi,CoNi conformation (one of the four pyrazolyl units is outwardly oriented). Two types of
300

Cu atoms are present (see Fig. 8a and 8b). Although both Cu centres are tetra coordinated with their coordination sphere composed of two Br- anions and two N atoms of two pyrazolyl units belonging to two consecutive tectons 2, they differ considerably by their coordination geometry. Indeed, whereas as one of the Cu atom adopts an almost tetrahedral coordination geometry (dCu-N of 1.97 and 1.96 , dCu-Br of 2.37 , NCuN angle of 130.0 and BrCuBr angle of 135.5), the coordination geometry of the other is almost square planar (dCu-N of 1.80 and 1.98 , dCu-Br of 2.33 , NCuN angle of 166.6 and BrCuBr angle of 169.0). Consequently two different distances between Cu atoms with the 1-D network are observed (8.03 and 9.96 )

305

Fig. 6: TGA analysis of solvated crystals of [2-(CoCl2)]n (red) and of

[2-(ZnCl2)]n (blue) between 30 C and 400 C (under N2, rate scan 2

265

/min). Whereas in the case of Co based network the solvent mixture was dichloroethane-ethanol, for the Zn based coordination polymer, a mixture of dichloroethane-methanol was used.
310

In both cases, the uptake of solvent molecules was also studied by

270

TGA measurements. In order to evacuate the solvent molecules and to avoid decomposition, the sample was first heated to 220 C under nitrogen flow and then allowed to cool to room temperature. The desolvated samples were exposed to different solvents (CH2Cl2, CHCl3, ClCH2C-CH2Cl, MeOH and EtOH) either in the liquid or vapour phase for 24 hours. TGA analysis showed in both cases the absence of solvent uptake. A possible reason for this observation could be the loss of structural integrity. Indeed, it was observed that after the complete removal of solvent molecules, the material appeared as crystalline however crystals were strongly striated. In order to investigate the crystallinity of samples, they were studied by both X-ray diffraction on single crystal and on power. Both techniques revealed the complete loss of order and crystallinity.

275

280

285

Surprisingly, the combination of 2 with CuBr2 leads to a different architecture. Indeed, the X-ray diffraction on single crystal revealed the formation of 1-D network (Fig. 8). The network belongs to the category of 1-D tubular architectures (Fig. 1d). We
290 315

a)

b)

Fig. 8: A portion of the 1-D coordination network generated upon combining the tecton 2 with CuBr2. For differentiating the geometry of the two non-equivalent Cu centres, two different views are presented. H atoms and solvent molecules are omitted for clarity. For bond distances and angles see text.

have previously observed the formation of such networks using either calixarene derivative19 or cyclophane type tectons bearing 4 nitrile or pyridine groups.7,10 The brownish crystal (monoclinic,
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320

In

conclusion,

the

neutral

tecton

2,

based

on
365

18.14, 17.1. Calc. for C56H64N8.0,5H2O (MW= 867.16): C 78.47, H 7.53, N 13.07 % found: C 78.27, H 7.65, N 12.98. Crystallisation: Crystals of 2: in a crystallisation tube (15 cm height, 0.4 cm diameter), upon slow diffusion at room temperature of Et2O (5
370

[1111]metacyclophane as a backbone adopting the blocked 1,3alternate conformation equipped with four pyrazolyl coordinating groups leads to the formation of 4 analogous neutral 2-D networks. The later are packed along the c-axis in staggered
325

fashion leading to 4 isostructural porous crystals. The crystalline materials are not robust and upon removal of solvent molecules, they lose to structural integrity. Unexpectedly, the same tecton leads to the formation of 1-D networks in the presence of CuBr2 complex. In order to increase the robustness of the crystalline material, we currently pursue our effort by combining the tecton 2 with other metal centres.
375

mL) into a CHCl3 solution (1 mL) of 2 (4 mg), colourless crystals were obtained after ca 3 days. Dark blue crystals of 2-CoX2 (X= Cl or Br) were obtained at room temperature in a crystallisation tube (15 cm height, 0.4 cm diameter) upon slow diffusion of 1.5 ml of an EtOH solution containing 1 mg of the metallic salt into 1 ml of a CH2Cl2 solution containing 2 mg of the compound 2 after ca 3 days. Colourless crystals of 2-MX2 (M = Zn, X = Cl or Br) brownish crystals of 2-CuBr2 were obtained at room temperature in a crystallisation tube (15 cm height, 0.4 cm diameter) upon slow diffusion of 1.5 ml of a mixture of MeOH-EtOH (1:1) containing 1 mg of the metallic salt into 1 ml of a 1,2-dichloroethane solution containing 2 mg of 2. Crystallography: Data were collected at 173(2) K on a Bruker APEX8 CCD Diffractometer equipped with an Oxford Cryosystem liquid N2 device, using graphite-monochromated Mo-K ( = 0.71073) radiation. The structures were solved using SHELXS-97 and refined by full matrix least-squares on F2 using SHELXL-97.20 The hydrogen atoms were introduced at calculated positions and not refined (riding model). All hydrogen atoms have been calculated except those connected to disordered atoms. Because of the disorder of the solvent molecules, the squeeze command 18 was used. In several cases, the diffraction power of crystals generated was rather low. Consequently, the R factors obtained are rather high. However, this does not affect significantly the structural descriptions of the networks reported. CCDC ???????? contains the supplementary crystallographic data. These data can be obtained free of or charge from at the www.ccdc.cam.ac.uk/conts/retrieving.html

330

Experimental
General: All reagents were purchased from commercial sources
335

and used without further purification except for pyrrole that was purified on an alumina pad. H NMR spectra were recorded at room temperature on a Bruker (300 MHz) NMR spectrometer. UV-Vis absorption measurements were carried out on a UVIKON XL, Bio-Tek. Spectrometer. Microanalyses were performed by the Service de Microanalyses de la Fdration de Recherche de Chimie, Universit de Strasbourg, Strasbourg. Synthesis Synthesis of 2: Under inert atmosphere and at room temperature, to a solution of sodium hydride (60% in oil) (335 mg, 8.3 mmol) in 50 ml of anhydrous DMF pyrazol (570 mg, 8.37 mmol) was added and the mixture was stirred for 90 minutes before compound 1
17
390 385

380

340

345

(500 mg, 0.69 mmol) and a spatula of sodium

iodide were slowly added. The solution was heated for 24 hours at 95 C and after cooling to room temperatures, DMF was
350

removed under vacuum and the crude product dissolved in 50 ml of CH2Cl2. The organic layer was washed with saturated aqueous NaHCO3 solution (50 ml) and twice with 50 ml of water before it was dried over MgSO4. The mixture was evaporated to dryness. The slightly yellow solid thus obtained was dissolved in a mixture of CH2Cl2 (10 ml) and MeOH (2 ml). 50 ml Et2O was added and the solution was cooled in an ice bath for 2 hours. The pure compound 2 (428 mg) was obtained in 73 % yield after filtration of the precipitate. H-NMR (CDCl3, 300 MHz, 25C, in ppm): 7.56 (d, 4H, Pyr-H, J = 1.8 Hz), 6.87 (d, 4H, Pyr-H, J = 2.4 Hz), 6.15 (t, 4H, Pyr-H, J1 = 1.8 Hz, J2 = 2.4 Hz), 5.44 (s, 8H, Ph-CH2-Pyr), 4.06 (s, 8H, Ph-CH2-Ph), 2.36 (s, 24H, o-CH3), 1.21 (s, 12H, m-CH3);
13
405 400 395

355

Cambridge Crystallographic data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: (Internat.) +44-1223/336-033; Email: deposit@ccdc.cam.ac.uk. Crystallographic data for 2: C112.50H128.50Cl1.50N16, M = 1757.99, Triclinic, a = 10.6861(10), b = 12.9999(11) , c = 17.5540(15) , = 88.348(2), = 88.849(1), = 78.015(2), U = 2384.2(4) 3, Space group P-1, Z = 1, = 0.113 mm-1, Refls measured:
This journal is The Royal Society of Chemistry [year]

360

C-RMN (CDCl3, 300 MHz, 25C, in

ppm): 139.2, 138.2, 136.2, 133.8, 129.4, 127.5, 104.9, 51.6, 33.1,
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17623, Independent Refls: 9998 [R(int) = 0.0286], Final R indices [I>2sigma(I)]: R1 = 0.0920, wR2 = 0.2594, GOF = 1.106, R indices (all data) R1 = 0.1473, wR2 = 0.3126.
410

450

are acknowledged for financial support and for a scholarship to J. E. References

Crystallographic

data

for

[2-(CoCl2)]

(SQUEEZE):
1
455

C28H32Cl2CoN4 (EtOH-1,2-dochloroethane solvate), M = 554.41, Orthorhombic, a = 26.3351(17), b = 20.7619(17) , c = 16.0893(13) , U = 8797.1(12) 3, Space group Pbcn, Z = 8, = 0.526 mm-1, Refls measured: 45247, Independent Refls: 8420
415

B. F. Abrahams, B. F. Hoskins and R. Robson, J. Am. Chem. Soc., (a) M. Simard, D. Su and J. D. Wuest, J. Am. Chem. Soc., 1991, 113, (a) M. W. Hosseini, Acc. Chem. Res., 2005, 38, 313; (b) M. W. (a) S. R. Batten and R. Robson, Angew. Chem. Int. Ed., 1998, 37,

1991, 113, 3606. 2 3 4 4696; (b) S. Mann, Nature, 1993, 365, 499. Hosseini, Cryst. Eng. Comm., 2004, 6, 318.

[R(int) = 0.0844], R1 = 0.0638, wR2 = 0.1247, GOF = 1.055, R indices (all data) R1 = 0.1489, wR2 = 0.1323. Crystallographic data for [2-(CoBr2)] (SQUEEZE): C28H32Br2CoN4 (EtOH-1,2-dochloroethane solvate), M = 643.33, Orthorhombic, a = 26.3921(8), b = 20.8329(7) , c = 16.2704(5) , U = 8945.9(5) , Space group Pbcn, Z = 8, = 2.185 mm , Refls measured: 65983, Independent Refls: 10294 [R(int) = 0.0400], R1 = 0.0645, wR2 = 0.1439, GOF = 1.034, R indices (all data) R1 = 0.1618, wR2 = 0.1558. Crystallographic data for [2-(ZnCl2)] (SQUEEZE): solvate), M =
470 465 460

1460; (b) A. J. Blake, N. R. Champness, P. Hubberstey, W.-S. Li, M. A. Withersby and M. Schrder, Coord. Chem. Rev., 1999, 193, 117; (c) M. W. Hosseini, in NATO ASI Series, Eds. D. Braga, F. Grepiono, G. Orpen, Serie c, Kluwer, Dordrecht, Netherlands, 1999, 538, 181; (d) B. Moulton and M.J. Zaworotko, Chem. Rev., 2001, 101, 1629; (e) M. Eddaoui, D.B. Moler, H. Li, B. Chen, T.M. Reineke, M. OKeeffe and O.M. Yaghi, Acc. Chem. Res., 2001, 34, 319; (f) G. F. Swiergers and T. J. Malefetse, Chem. Rev., 2000, 100, 3483; (g) C. Janiak, Dalton Trans., 2003, 2781; (h) L. Carlucci, G. Ciani and D. M. Proserpio, Coord. Chem. Rev., 2003, 246, 247; (i) S. Kitagawa, Angew. Chem. Int Ed., 2004, 43, 2434; (j) G. Frey, C. Mellot-Draznieks, C. Serre and F. Millange, Acc. Chem. Res., 2005, 38, 218; (k) D. Bradshaw, J. B. Claridge, E. J. Cussen, T. J. Prior and M. J. Rosseinsky, Acc. Chem. Res., 2005, 38, 273; (l) G. Ferey, Chem. Soc. Rev., 2008, 37, 191.
475

420

-1

425

C28H32Cl2ZnN4

(MeOH-1,2-dochloroethane

560.85, Orthorhombic, a = 26.4215(19), b = 20.6802(16) , c = 16.0503(12) , U = 8769.9(11) 3, Space group Pbcn, Z = 8, = 0.697 mm-1, Refls measured: 54882, Independent Refls: 10108 [R(int) = 0.0946], R1 = 0.0647, wR2 = 0.1690, GOF = 1.010, R
430

P. Grosshans, A. Jouaiti, V. Bulach, J.-M. Planeix, M. W. Hosseini, N. Kyritsakas, Eur. J. Inorg Chem., 2004, 453; P. Grosshans, A. Jouaiti, M. W. Hosseini, A. De Cian, N. Kyritsakas-Gruber, Tetrahedron Lett., 2003, 44, 1457; V. Jullien, M. W. Hosseini, J.-M. Planeix, A. De Cian, J. Organomet. Chem., 2002, 643-644, 376; A. Jouaiti, M. Lo, M. W. Hosseini, A. De Cian, Chem. Commun., 2000, 2085; M. Lo, M. W. Hosseini, A. Jouaiti, A. De Cian, J. Fischer, Eur. J. Inorg. Chem., 1999, 1981; R. Schneider, M. W. Hosseini, J.-M. Planeix, A. De Cian, J. Fischer, Chem. Commun., 1998, 1625; E. Deiters, V. Bulach, M. W. Hosseini, New J. Chem., 2006, 30, 1289.

indices (all data) R1 = 0.1205, wR2 = 0.1813. Crystallographic data for [2-(ZnBr2)] (SQUEEZE): C28H32Cl2ZnN4 (MeOH-1,2-dochloroethane solvate), M = 649.77, Orthorhombic, a = 26.3680(10), b =
3

20.8457(8) , c =
480

16.2776(7) , U = 8947.1(6) , Space group Pbcn, Z = 8, =

435

2.350 mm-1, Refls measured: 66838, Independent Refls: 10294 [R(int) = 0.0971], R1 = 0.0642, wR2 = 0.1429, GOF = 1.018, R indices (all data) R1 = 0.1441, wR2 = 0.1554. Crystallographic data for [2-(CuBr2)] (SQUEEZE):
485

S. Pappalardo, G. Ferguson, J. F. Gallagher, J. Org. Chem., 1992, 57, 7102; F. Bottino, G. Montaudo, P. Maravigna, Ann. Chimica, 1967, 57, 972; S. Pappalardo, F. Bottino, Phosphorus and Sulfur, 1984, 19, 327.

C56H64Br4Cu2N8, M = 1295.87, Monoclinic, a = 21.815(2), b =

440

14.8140(17) , c = 22.496(3), = 97.717(7), , U = 7204.1(14) 3, Space group P2/c, Z = 4, = 2.843 mm-1, Refls measured: 51944, Independent Refls: 15895 [R(int) = 0.0900], R1 = 0.1509, wR2 = 0.3734, GOF = 1.057, R indices (all data) R1 = 0.2414, wR2 = 0.4162.
490

7 8 9

C. Klein, E. Graf, M. W. Hosseini, A. De Cian, J. Fischer, Chem. Comm., 2000, 239. X. Delaigue, M. W. Hosseini, Tetrahedron Lett., 1994, 35, 8111. C. Klein, E. Graf, M. W. Hosseini, A. De Cian, N. J. Chem., 2001, 25, 207.

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Acknowledgements Universit de Strasbourg, the International Centre for Frontier Research in Chemistry (FRC), Strasbourg, Institut Universitaire de France, the CNRS and the Ministry of Education and Research
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495

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Graphical abstract
The combination of a [1111]metacyclophane bearing four pyrazoly groups with MX2 (M = Co, Zn, Cu; X ????= Cl, Br) complexes leads to the formation of 1- and 2-D neutral coordination networks.

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